KR102283435B1 - Amorphous material and the use thereof - Google Patents

Abstract

The present invention relates to novel amorphous materials having advantageous properties as charge transport materials and/or absorber materials for various applications, in particular photoelectric conversion devices, i.e. an amorphous material of the composition of the formula (I):
Formula I
(R ¹ NR ² ₃ ) ₅ MeX ¹ _a X ² _b
In the above formula,
R ¹ is C ₁ -C ₄ -alkyl;
R ² are independently of each other hydrogen or C ₁ -C ₄ -alkyl;
Me is a divalent metal;
X ¹ and X ² have different meanings and are each independently selected from F, Cl, Br, I and pseudohalides;
a and b are each independently 0 to 7, and the sum of a and b is 7.

Description

Amorphous substances and uses thereof

The present invention relates to novel amorphous materials with advantageous properties as charge transport materials and/or absorber materials for various applications, in particular photoelectric conversion devices.

Dye-sensitized photoelectric conversion devices (dye-sensitized solar cells, DSCs) have attracted great interest in recent years. They have several advantages compared to silicon-based solar cells, such as lower production and material costs (since cheap metal oxide semiconductors such as titanium dioxide can be used without purification for high purity). Other advantages include their flexibility, transparency and light weight. The overall performance of a photoelectric conversion element _{is characterized by several variables such as open circuit voltage (V oc} ), short-circuit current (I _sc ), charge factor (FF) and the resulting energy conversion efficiency (η). Dye-sensitized solar cells are currently one of the most efficient alternative solar cell technologies. There continues to be a need to further improve the performance of solid dye-sensitized photoelectric conversion devices, specifically their energy conversion efficiency (η).

The construction of DSCs is generally based on a transparent conductive layer, a transparent substrate (eg glass) coated with a working electrode. An n-conducting metal oxide, for example a layer of nanoporous titanium dioxide (TiO ₂ ) of about 2 to 20 μm thick, is generally applied at or in the vicinity of this electrode. Again, on its surface, a monolayer of a photosensitive dye, such as a ruthenium complex or an organic dye, is typically adsorbed, which can be converted to an excited state by absorption. The counter electrode may optionally have a catalyst layer of a metal (eg platinum) having a thickness of several μm. The function of DSC is based on the fact that light is absorbed by the dye and electrons are transferred from the excited dye to the n-semiconducting metal oxide semiconductor and travel over it to the anode. In liquid DSC, the region between the two electrodes _{is filled with a solution of a redox electrolyte, such as iodine (I 2} ) and lithium iodide (LiI), in which photocurrent can be collected at the front and back contacts of the cell. let it be

In liquid transformation of DSC, efficiencies of greater than 12% have been reported (eg, Graetzel et al., Science 2011, 334, 629 - 634). Nevertheless, cells comprising liquid electrolytes have special drawbacks that prevent widespread use of this technology. Therefore, in many cases, liquid DSCs have durability problems due to the use of organic liquid electrolytes that cause serious problems such as electrode corrosion and electrolyte leakage. Therefore, suitable substitutes that can be used for hole conduction instead of liquid electrolytes have been investigated. Accordingly, various materials have been studied for their suitability as solid electrolytes/p-semiconductors.

A novel development in the production of solid DSCs is the use of organometallic perovskite as light-collecting compounds (perovskite sensitized solar cells, PSCs). Literature [H.-S. Kim et al., Scientific Reports, 2:59, DOI: 10.1038/srep00591 describe lead iodide perovskite-sensitized solar cells with efficiencies greater than 9%. In this cell, perovskite nanoparticles of methyl ammonium lead iodide are _{used as absorber material together with mesoporous TiO 2} as a transparent n-type semiconductor and spiro-MeOTAD as a p-type hole semiconductor.

MM Lee, J. Teuscher, T. Miyasaki, TN Murakami and HJ Snaith, Sciencexpress, 4 October 2012, 10.1126 / science. 1228604, methylammonium lead iodide chloride (CH _{3 ) as a crystalline perovskite absorbent material} A hybrid solar cell based on _{NH 3} PbI _{2 Cl) is described.} In these cells, mesoporous alumina is used instead of titanium dioxide. In these cells, Al ₂ O ₃ acts not as an n-type oxide, but as a meso-scale “scaffold” on which the device is built. Thus, the authors no longer refer to devices as "sensitized" solar cells, but as two-component hybrid solar cells or "meso-superstructured solar cells".

It is an object of the present invention to provide novel compounds which can be advantageously used for transporting charges and/or as absorbent materials in various fields. Specifically, the novel compound should be suitable for the manufacture of photoelectric conversion devices. In addition, the material must be easy to process, for example by a film building process.

Surprisingly, it has been found that this object is achieved by the novel amorphous material of the present invention.

According to a first aspect of the present invention, there is provided an amorphous material of the composition of formula (I):

[Formula I]

(R ¹ NR ² ₃ ) ₅ MeX ¹ _a X ² _b

In the above formula,

R ¹ is C ₁ -C ₄ -alkyl;

R ² are independently of each other hydrogen or C ₁ -C ₄ -alkyl;

Me is a divalent metal;

X ¹ and X ² have different meanings and are each independently selected from F, Cl, Br, I and pseudohalides;

a and b are each independently 0 to 7, and the sum of a and b is 7.

A preferred embodiment is (CH ₃ NH ₃ ) ₅ PbI _{3 . 5} Cl _{3 .5} or (CH ₃ NH ₃ ) ₅ SnI _{3 . 5} is an amorphous material of a composition of Cl _{3 .5.}

A further object of the present invention relates to a composition comprising an amorphous material as defined above and below and at least one different component.

A further object of the present invention is the preparation of an amorphous material of the composition of the formula (I), comprising the step of reacting a compound of the formula (1), a compound of the formula How to:

[Formula 1]

(R ¹ NR ² ₃ )X ¹

[Formula 2]

(R ¹ NR ² ₃ )X ²

[Formula 3]

MeX ² ₂

Formula I

(R ¹ NR ² ₃ ) ₅ MeX ¹ _a X ² _b

In the above formula,

R ¹ is C ₁ -C ₄ -alkyl;

R ² are independently of each other hydrogen or C ₁ -C ₄ -alkyl;

Me is a divalent metal;

X ¹ and X ² have different meanings and are each independently selected from F, Cl, Br, I and pseudohalides;

a and b are each independently 0 to 7, and the sum of a and b is 7.

A further object of the present invention relates to a photoelectric conversion device comprising an amorphous material as defined above and below, or a composition comprising such material.

A particular aspect includes an electrically conductive layer that is part of or forms the working electrode (anode); a photosensitive layer comprising an absorber material and optionally comprising a semiconducting metal oxide (which may act as an electron transport material) or an insulating material (which may act as a scaffold); charge transfer layer; and an electrically conductive layer that is part of or forms a counter electrode (cathode), wherein the photosensitive layer and/or the charge transport layer comprises one or more of the above and the following amorphous materials or such materials It is a photoelectric conversion element containing.

A further object of the invention relates to a solar cell comprising the photoelectric conversion element of the invention.

A further object of the present invention is a field effect transistor (FET) comprising a substrate having at least one gate structure, a source electrode and a drain electrode, and at least one amorphous material as defined herein, or a composition as defined herein comprising such material. is about

A further object of the present invention relates to a substrate comprising a plurality of field effect transistors (FETs), wherein at least some of the field effect transistors are one or more amorphous materials as defined herein, or as defined herein comprising such materials. composition.

A further object of the present invention relates to an electroluminescent device comprising an upper electrode, a lower electrode, wherein at least one of said electrodes is transparent, an electroluminescent layer and optionally an auxiliary layer, wherein said electroluminescent device comprises: one or more amorphous substances as defined in, or a composition as defined herein comprising such substances. Specifically, the electroluminescent device is a light emitting diode (LED).

A further object of the present invention is as or in a semiconducting layer of a thin film transistor (TFT), as or in a semiconducting layer of a light emitting diode (LED), as or in a phosphor material of an LED, or in a battery, a rechargeable battery (accumulator) ), etc., to the use of an amorphous material as defined above and below or a composition comprising such material.

1 shows the XRD of an extract mixture at room temperature (20° C.) before heating.
2 shows the XRD of the reaction mixture at 140° C. showing no reflection, indicative of the melt.
3 shows the DSC measurements confirming the thermal behavior and also showing no mass loss.

Alternatively, the amorphous material may be described as 5(R ¹ NR ² ₃ ): 1Me: aX ¹ : bX ² .

In the context of the present invention, the expression "amorphous material" denotes a material (eg glass) that does not produce sharp diffraction peaks in X-ray powder diffraction (XRD).

The expression "halogen" denotes in each case fluorine, bromine, chlorine or iodine, in particular chlorine, bromine or iodine.

Suitable pseudohalides are, for example, CN, SCN, OCN, N ₃ and the like.

Suitable C ₁ -C ₄ -alkyl groups are in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.

Preferably, R ¹ is methyl or ethyl. Specifically, R ¹ is methyl.

Preferably, ^{both R 2} groups are hydrogen.

Preferably, Me is selected from Pb, Sn, Fe, Zn, Cd, Co, Cu, Ni, Mn and mixtures thereof. More preferably, Me is selected from Pb, Sn and mixtures thereof. Specifically, Me is Pb.

In a preferred embodiment of the amorphous material according to the invention, X ¹ is I and X ² is Cl.

Preferably, a and b are both 0.1 to 6.9, more preferably 0.5 to 6.5, specifically 1 to 6. In a preferred embodiment of the amorphous material according to the invention, a and b are both 3.5.

A particular embodiment is (CH ₃ NH ₃ ) ₅ PbI _{3 . 5} Cl _{3 .5} or (CH ₃ NH ₃ ) ₅ SnI _{3 . 5} is an amorphous material of a composition of Cl _{3 .5.}

A further object of the present invention relates to a composition comprising an amorphous material as defined above and below and at least one different component. Suitable additional components are amorphous or crystalline components (specifically based on at least some of the elements present in the amorphous material of the present invention).

A further object of the present invention is the preparation of an amorphous material of the composition of the formula (I), comprising the step of reacting a compound of the formula (1), a compound of the formula How to:

Formula 1

(R ¹ NR ² ₃ )X ¹

Formula 2

(R ¹ NR ² ₃ )X ²

Formula 3

MeX ² ₂

Formula I

(R ¹ NR ² ₃ ) ₅ MeX ¹ _a X ² _b

In the above formula,

R ¹ is C ₁ -C ₄ -alkyl;

R ² are independently of each other hydrogen or C ₁ -C ₄ -alkyl;

Me is a divalent metal;

X ¹ and X ² have different meanings and are each independently selected from F, Cl, Br, I and pseudohalides;

a and b are each independently 0 to 7, and the sum of a and b is 7.

Preferably, the components are mixed in a ratio corresponding to the stoichiometric amounts of the elements of the composition ^{5(R 1} NR ² ₃ ) : 1Me : aX ¹ : bX ^{2 .}

In a particular embodiment, ^{the molar ratio of (R 1} NR ² ₃ )X ¹ : (R ¹ NR ² ₃ )X ² : MeX ² ₂ is about 3.5 : 1.5 : 1.

In a first aspect, the reaction is carried out in a melt. According to this embodiment, the reaction mixture is heated to a temperature above the melting point of the extract composition. When the reaction is carried out in a melt, the temperature is preferably 60 to 250°C, more preferably 80 to 200°C.

In a second embodiment, the reaction is carried out in the presence of a solvent. Suitable solvents are aprotic solvents. Suitable aprotic solvents are dimethylformamide, ethers such as dioxane and diglyme (bis(2-methoxyethyl) ether), N-methylpyrrolidone, (CH ₃ ) ₂ SO, dimethyl sulfone, sulfolane , cyclic ureas such as 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (DMPU), imidazolidin-2-one, acetonitrile, methoxyaceto nitriles or mixtures thereof. When the reaction is carried out in the presence of a solvent, the temperature is preferably 20 to 200°C, more preferably 40 to 100°C.

In a preferred embodiment, the reaction is carried out under an inert gas atmosphere. Suitable inert gases are, for example, nitrogen or argon.

A further object of the present invention relates to a photoelectric conversion element. Preferably, the photoelectric conversion element is a thin film photoelectric conversion element.

As noted above, a particular aspect includes an electrically conductive layer that is part of or forms the working electrode (anode); a photosensitive layer comprising an absorber material and optionally comprising a semiconducting metal oxide (which may act as an electron transport material) or an insulating material (which may act as a scaffold); charge transfer layer; and an electrically conductive layer that is part of or forms a counter electrode (cathode), wherein the photosensitive layer and/or the charge transport layer comprises one or more of the above and below defined amorphous materials or such materials. It is a photoelectric conversion element containing a composition.

In a preferred embodiment, the photosensitive layer comprises as absorber material at least one amorphous material as defined above and below, or a composition comprising such material. According to this aspect, it is not necessary for the photosensitive layer to further comprise a semiconducting metal oxide or insulating material.

In this embodiment, it is also possible for the charge transport layer to comprise at least one amorphous material according to the invention.

In a more preferred embodiment, the photosensitive layer comprises at least one perovskite material as absorber material. In this embodiment, the photosensitive layer may further comprise one or more amorphous materials as defined above and below or a composition comprising such materials.

In this embodiment, it is also possible for the charge transport layer to comprise at least one amorphous material according to the invention.

The absorber material may be deposited on a semiconducting metal oxide or insulating material (eg, insulating metal oxide). Suitable semiconducting metal oxides are those known for use in dye-sensitized photoelectric conversion devices, in particular TiO ₂ . A suitable insulating metal oxide that does not act as an n-type oxide is Al ₂ O ₃ .

In another preferred embodiment, the photoelectric conversion device according to the invention further comprises a hole-conducting layer between the charge transport layer and the cathode. Suitable materials used for the hole-conducting layer are, for example, 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenyl-amine)-9,9'-spirobifluorene ( "Spiro-MeOTAD").

A suitable method for manufacturing a photoelectric conversion device comprises the steps of:

i) providing an electrically conductive layer;

ii) optionally depositing an undercoat layer thereon;

iii) depositing a photosensitive layer on the electrically conductive layer obtained in step i), or, if present, the underlying coating layer obtained in step ii);

iv) depositing a charge transport layer on the photosensitive layer obtained in step iii); and

v) depositing a counter electrically conductive layer on the charge transport layer obtained in step iv).

The photosensitive layer and/or the charge transport layer comprises at least one amorphous material as defined above and below or a composition comprising such material.

The electrically conductive layer and/or the counter electrically conductive layer may be deposited on a substrate (also referred to as a support or carrier) to improve the strength of the photoelectric conversion element. In this context, a layer composed of an electrically conductive layer and a substrate on which said electrically conductive layer is deposited is referred to as a conductive support. A layer composed of a counter electrically conductive layer and a substrate on which the counter electrically conductive layer is optionally deposited is referred to as a counter electrode. Preferably, the electrically conductive layer and the substrate on which the electrically conductive layer is optionally deposited are transparent. The counter electrically conductive layer, and optionally also the support on which the counter electrically conductive layer is optionally deposited, may also be transparent, but it is not critical.

Each layer included in the photoelectric conversion element of the present invention will be described in detail below.

(A) electrically conductive layer [step (i)]

The electrically conductive layer is stable enough to support the remaining layers, or the electrically conductive material forming the electrically conductive layer is deposited on a substrate (also referred to as a support or carrier). Preferably, the electrically conductive material forming the electrically conductive layer is deposited on a substrate. The combination of electrically conductive materials deposited on a substrate is hereinafter referred to as a "conductive support".

In the first case, the electrically conductive layer is preferably a material having sufficient strength and capable of sufficiently sealing the photoelectric conversion element, for example metals such as platinum, gold, silver, copper, zinc, titanium, aluminum and these made of an alloy composed of

In the second case, the substrate on which the electrically conductive layer containing the electrically conductive material is generally deposited is in the opposite direction to the photosensitive layer, with the result that the electrically conductive layer is in direct contact with the photosensitive layer.

Preferred examples of the electrically conductive material include metals such as platinum, gold, silver, copper, zinc, titanium, aluminum, indium and alloys composed of these; carbon (especially in the form of carbon nanotubes); and electrically conductive metal oxides, especially transparent conductive oxides (TCO), such as indium-tin composite oxide, tin oxide doped with fluorine, antimony or indium, and zinc oxide doped with aluminum. In the case of metals, they are usually used in the form of thin films, resulting in a sufficiently transparent layer. More preferably, the electrically conductive material is selected from transparent conductive oxides (TCOs). Of these, tin oxide doped with fluorine, antimony or indium, and indium-tin oxide (ITO) are preferred, tin oxide doped with fluorine, antimony or indium is more preferred, and tin oxide doped with fluorine is particularly preferred. do. Specifically, the tin oxide is SnO ₂ .

The electrically conductive layer preferably has a thickness of 0.02 to 10 μm, more preferably 0.1 to 1 μm.

Generally, the light will be irradiated from the side of the electrically conductive layer (not from the side of the opposite electrically conductive layer). Accordingly, as already mentioned, it is preferred that the support with the electrically conductive layer, preferably the entire conductive support, is substantially transparent. As used herein, the term "substantially transparent" means that the light transmittance is 50% or more with respect to light in the visible region to the near infrared region (400 to 1,000 nm). The light transmittance is preferably 60% or more, more preferably 70% or more, specifically 80% or more. The conductive support particularly preferably has a high light transmittance to light for which the photosensitive layer is sensitive.

The substrate can be made of glass, such as soda glass (which has good strength) and non-alkaline glass (which is not affected by alkaline elution). Alternatively, a transparent polymer film may be used as the substrate. The materials used for the polymer film were tetraacetyl cellulose (TAC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), syndiotactic polystyrene (SPS), polyphenylenesulfide (PPS), polycarbonate (PC). , polyarylate (PAr), polysulfone (PSF), polyestersulfone (PES), polyimide (PI), polyetherimide (PEI), cyclic polyolefin, brominated phenoxy resin, and the like.

The conductive support is preferably prepared by depositing an electrically conductive material onto a substrate by liquid coating or vapor deposition.

The amount of electrically conductive material deposited on the substrate is selected to ensure sufficient transparency. Suitable amounts will vary depending on the conductive material and substrate used and will be determined on a case-by-case basis. For example, in the case of TCO as conductive material and glass as substrate, the amount may be from ^{0.01 to 100 g/m 2 .}

Metallic lead is preferably used to reduce the resistance of the conductive support. The metallic lead is preferably made of a metal, such as platinum, gold, nickel, titanium, aluminum, copper, silver, or the like. It is preferable that the metallic lead is provided on the substrate on which the electrically conductive layer is deposited, by a vapor deposition method, a sputtering method, or the like. The reduction in the amount of incident light due to the metallic lead is preferably limited to 10% or more, more preferably 1 to 5% or more.

(B) undercoat layer (“buffer layer”) [optional step (ii)]

The layer obtained in step (i) may be coated with a buffer layer. The purpose is to avoid direct contact of the charge transport layer with the electrically conductive layer, and thus to prevent a short circuit, in particular when the charge transport layer is a solid hole-transport material.

This “undercoat” or buffer layer material is preferably a metal oxide. The metal oxides are preferably from titanium, tin, zinc, iron, tungsten, vanadium and niobium oxides (eg TiO ₂ , SnO ₂ , Fe ₂ O ₃ , WO ₃ , ZnO, V ₂ O ₅ or Nb ₂ O ₅ ). selected, more preferably TiO ₂ .

The undercoating layer is described, for example, in Electrochim. Acta, 40, 643 to 652 (1995), or, for example, Thin Solid Films 445, 251-258 (2003), Surf. Coat. Technol. 200, 967 to 971 (2005) or Coord. Chem. Rev. 248 (2004), 1479.

The thickness of the lower coating layer is preferably from 5 to 1,000 nm, more preferably from 10 to 500 nm, specifically from 10 to 200 nm.

(C) photosensitive layer [step (iii)]

In a first preferred embodiment, the photosensitive layer comprises at least one amorphous material according to the invention or a composition comprising such material. In this embodiment, it is not necessary for the photosensitive layer to further comprise a semiconducting metal oxide or insulating material.

In a second preferred embodiment, the photosensitive layer comprises at least one perovskite material as absorber material, and a semiconducting metal oxide or carrier material that does not act as an n-type oxide. In this embodiment, the photosensitive layer and/or the charge transport layer (see (D) below) comprises at least one amorphous material according to the invention or a composition comprising such material.

(1) semiconducting metal oxide

An n-type semiconductor is preferably used in the present invention, and conduction band electrons act as carriers under photo-excitation conditions to provide the anode current.

Suitable semiconducting metal oxides are generally all metal oxides known to be useful on organic solar cells. These include oxides of titanium, tin, zinc, iron, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, cesium, niobium or tantalum. Also, composite semiconductors such as M ¹ _x M ² _y O _z may be used in the present invention, wherein M, M ¹ and M ² independently represent a metal atom, O represents an oxygen atom, and x, y and z represents numbers that combine with each other to form neutral molecules. Examples are TiO ₂ , SnO ₂ , Fe ₂ O ₃ , WO ₃ , ZnO, Nb ₂ O ₅ , SrTiO ₃ , Ta ₂ O ₅ , Cs ₂ O, zinc stannate, complex oxides of the perovskite type, such as barium titanates, and binary and ternary iron oxides.

Preferred semiconducting metal oxides are selected from TiO ₂ , SnO ₂ , Fe ₂ O ₃ , WO ₃ , ZnO, Nb ₂ O ₅ and SrTiO ₃ . Among these semiconductors, TiO ₂ , SnO ₂ , ZnO and mixtures thereof are more preferred. TiO ₂ , ZnO and mixtures thereof are even more preferred, TiO ₂ being particularly preferred.

The metal oxide is preferably present in amorphous or nanocrystalline form. More preferably, they are present as nanocrystalline porous layers. The metal oxide layer may also be present in a structured form, such as nanorods.

When more than one metal oxide is used, more than two metal oxides may be applied as a mixture when the photosensitive layer is formed. Alternatively, the layer of metal oxide may be coated with one or more different metal oxides.

The metal oxide may also be present as a layer on a different semiconductor, such as GaP, ZnP or ZnS.

_{TiO 2} and ZnO used in the present invention preferably have an anatase-like crystal structure, and are also preferably nanocrystalline.

A semiconductor may or may not include a dopant to increase its electronic conductivity. Preferred dopants are metal compounds such as metals, metal salts and metal chalcogenides.

In the photosensitive layer, the semiconducting metal oxide layer is preferably porous, particularly preferably nanoporous, in particular mesoporous.

Porous materials are characterized by a porous, non-smooth surface. Porosity is a measure of the void space in a material and is the fraction of the volume of the voids to the total volume. The nanoporous material has pores with a diameter in the nm range, ie about 0.2 to 1,000 nm, preferably 0.2 to 100 nm. A mesoporous material is a specific form of nanoporous material having pores with a diameter of 2 to 50 nm. "Diameter" in this context refers to the largest dimension of the void. The diameter of the pores can be measured by a number of porosimetry methods, such as optical methods, absorption methods, water evaporation methods, mercury intrusion porosimetry or gas expansion methods.

The particle size of the semiconducting metal oxide used in the preparation of the semiconducting metal oxide layer is generally in the range from nm to μm. The average size of the primary semiconductor particles obtained from the diameter of a circle equivalent to the protruding region is preferably 200 nm or less, such as 5 to 200 nm, more preferably 100 nm or less, such as 5 to 100 nm or 8 to 100 nm. am.

Two or more semiconducting metal oxides having different particle size distributions may be mixed in the preparation of the photosensitive layer. In this case, the average particle size of the smaller particles is preferably 25 nm or less, more preferably 10 nm or less. In order to improve the light-capture rate of the photoelectric conversion element by scattering the incident light, a semiconducting metal oxide having a large particle size, for example, a diameter of about 100 to 300 nm can be used for the photosensitive layer.

See, for example, Materia, Vol. 35, No. 9, Page 1012 to 1018 (1996)] is preferred as a method for producing a semiconducting metal oxide. Also preferred is a process comprising preparing the oxide by subjecting the chloride to high temperature hydrolysis in an oxyhydrogen salt.

When titanium oxide is used as the semiconducting metal oxide, the above-mentioned sol-gel method, gel-sol method, and high-temperature hydrolysis method are preferably used. Among the sol-gel methods, Barbe et al., Journal of American Ceramic Society, vol. 80, no. 12, page 3157 to 3171 (1997) and Burnside et al., Chemistry of Materials, vol. 10, no. 9, pages 2419 to 2425 (1998), are also preferred.

The semiconducting metal oxide is coated on the layer obtained in step (i), or, if carried out, step (ii), the layer obtained in step (i) or (ii) is coated with a dispersion or colloidal solution containing particles method, the above-mentioned sol-gel method, and the like. The wet type layer forming method is relatively advantageous for mass production of photoelectric conversion elements, improvement of properties of semiconducting metal oxide dispersions, improvement of adaptability of the layer obtained in step (i) or (ii), and the like. As such, the wet type layer forming method, the coating method, the printing method, the electrolytic electrodeposition method and the electrodeposition technique are typical examples. In addition, the semiconducting metal oxide layer may be formed of metal oxide; LPD (liquid phase deposition) method in which a metal solution undergoes ligand exchange or the like; sputtering method; PVD (Physical Vapor Deposition) method; CVD (chemical vapor deposition) method; Alternatively, it may be disposed by an SPD (spray pyrolysis deposition) method in which a pyrolysis-type metal oxide precursor is sprayed onto a heated substrate to produce a metal oxide.

The dispersion containing the semiconducting metal oxide may be prepared by the above-mentioned sol-gel method; semiconductor grinding in mortar; dispersion of semiconductors while grinding in a mill; It can be prepared by synthesizing and precipitating a semiconducting metal oxide in a solvent.

As the dispersion solvent, water or an organic solvent such as methanol, ethanol, isopropyl alcohol, citronellol, terpineol, dichloromethane, acetone, acetonitrile, ethyl acetate, etc., mixtures thereof and at least one of the above organic solvents A mixture of and water may be used. Polymers such as polyethylene glycol, hydroxyethylcellulose and carboxymethylcellulose, surfactants, acids, chelating agents and the like can be used as dispersants, if necessary. Specifically, the viscosity of the dispersion and the porosity of the semiconducting metal oxide layer can be controlled by changing the molecular weight of polyethylene glycol, and since the semiconducting metal oxide layer containing polyethylene glycol is hardly peeled off, polyethylene glycol may be added to the dispersion. can

Preferred coating methods include, for example, the roller method and the dip method for applying the semiconducting metal oxide, and the air-knife method and the blade method, for example for conditioning the layer. include Also, as methods in which application and adjustment can be performed simultaneously, a wire-bar method, a slide-hopper method (such as described in U.S. Patent No. 2,761,791), an extrusion method, a curtain method and the like are preferred. Also, spin method and spray method can be used. Regarding the wet type printing method, relief printing, offset printing, gravure printing, intaglio printing, gum printing, screen printing, and the like are preferable. A preferred method for forming the layer may be selected from the above methods depending on the viscosity of the dispersion and the desired wet thickness.

The semiconducting metal oxide layer is not limited to a single layer. The dispersions each comprising a semiconducting metal oxide having a different particle size may be subjected to a multilayer coating. In addition, dispersions each containing different types of semiconducting metal oxides, binders or additives may be subjected to a multilayer coating. Multilayer coatings are also effectively used when the thickness of a single layer is insufficient.

In general, as the thickness of the semiconducting metal oxide layer, which is equal to the thickness of the photosensitive layer, increases, the amount of incorporated absorbent (eg, perovskite) per unit of protruding area increases, resulting in higher light - Causes catch rate. However, since the diffusion distance of the generated electrons also increases, a higher loss rate due to recombination of charges is expected. A preferred thickness of the semiconducting metal oxide layer is 0.1 to 100 μm, more preferably 0.1 to 50 μm, even more preferably 0.1 to 30 μm, specifically 0.1 to 20 μm, specifically 0.5 to 3 μm.

The coating amount of the semiconducting metal oxide per 1 m ² of the substrate is preferably 0.5 to 100 g, more preferably 3 to 50 g.

After applying the semiconducting metal oxide onto the layer obtained in step (i) or (ii), the obtained product is subjected to a heat treatment ( sintering step). The heating temperature is preferably 40 to 700°C, more preferably 100 to 600°C. The heating time is preferably from 10 minutes to 10 hours.

However, when the electrically conductive layer contains a heat-sensitive material having a low melting point or softening point, such as a polymer film, the product obtained after application of the semiconducting metal oxide does not undergo high-temperature treatment, since this may damage the substrate . In this case, the heat treatment is preferably carried out at a temperature as low as possible, for example at 50 to 350°C. In this case, the semiconducting metal oxide is preferably one with fewer particles, in particular one with a median particle size of 5 nm or less. Alternatively, the inorganic acid or metal oxide precursor may be heat-treated at such low temperatures.

Further, the heat treatment may be performed while applying ultraviolet rays, infrared rays, microwaves, electric fields, ultrasonic waves, etc. to the semiconducting metal oxide in order to reduce the heating temperature. In order to remove unnecessary organic compounds, etc., the heat treatment is preferably performed together with exhaust, oxygen plasma treatment, washing with pure water, solvent or gas, or the like.

If necessary, it is possible to form a blocking layer on the semiconducting metal oxide layer before contacting the semiconducting metal oxide layer with the absorbent in order to improve the performance of the semiconducting metal oxide layer. This barrier layer is usually introduced after the above-mentioned heat treatment. An example of forming the barrier layer is a semiconducting metal oxide layer in a solution of a metal alkoxide such as titanium ethoxide, titanium isopropoxide or titanium butoxide, chloride such as titanium chloride, tin chloride or zinc chloride, nitride or sulfide. impregnation, followed by drying or sintering of the substrate. For example, the blocking layer may be a metal oxide such as TiO ₂ , SiO ₂ , AI ₂ O ₃ , ZrO ₂ , MgO, SnO ₂ , ZnO, Eu ₂ O ₃ , Nb ₂ O ₅ or combinations thereof, TiCl ₄ , or made of a polymer such as poly(phenylene oxide-co-2-allylphenylene oxide) or poly(methylsiloxane). Details of the preparation of such layers can be found, for example, in Electrochimica Acta 40, 643, 1995; J. Am. Chem. Soc 125, 475, 2003]; See Chem. Lett. 35, 252, 2006]; Literature [J. Phys. Chem. B, 110, 1991, 2006]. Preferably, TiCl ₄ is used. The barrier layer is typically dense and dense, and is typically thinner than the semiconducting metal oxide layer.

(2) amorphous substances or compositions comprising such substances;

The amorphous material is preferably adsorbed to a material having a large surface area. Specifically, the amorphous material may be adsorbed to the semiconducting metal oxide.

Amorphous materials or compositions comprising such materials may be prepared by contacting these components with each other, for example by soaking the product obtained after application of a semiconducting metal oxide layer to a solution of the amorphous material or composition comprising such materials, or By applying the solution to the semiconducting metal oxide layer, it can be adsorbed to the semiconducting metal oxide. In the former case, a soaking method, a dipping method, a roller method, an air-knife method, etc. can be used. In the soaking method, the amorphous material or a composition comprising such material may be adsorbed at room temperature or under reflux with heating as described in Japanese Patent No. 7249790. As the application method in the latter case, a wire-bar method, a slide-hopper method, an extrusion method, a curtain method, a spin method, a spraying method and the like can be used. In addition, the amorphous material or composition can be applied to the semiconducting metal oxide layer by an ink-jet method onto an image, thereby providing the photosensitive layer with a surface having the shape of the image.

Where more than one amorphous material or a composition comprising such material is applied, the application of the two or more amorphous materials or a composition comprising such material can be carried out simultaneously, for example by using a mixture of two or more amorphous materials, or other amorphous materials. It can be done sequentially, by application of a material followed by application of one amorphous material.

Additionally or alternatively, an amorphous material or a composition comprising such material may be applied in conjunction with a charge transfer material.

(3) perovskite absorbent material

In principle, all perovskite absorbent materials known to the person skilled in the art can be used. The perovskite absorbent material is preferably an organometallic halide compound. Preference is given to compounds of the formula (R ^d NH ₃ )PbX ^a ₃ ^{, wherein R d} is C ₁ -C ₄ -alkyl and X ^a is Cl, Br or I. Particular preference is given to (CH ₃ NH _{3 )PbI 3} , (CH ₃ CH ₂ NH ₃ )PbI ₃ , (CH ₃ NH ₃ )PbI ₂ Cl and (CH ₃ CH ₂ NH ₃ )PbI ₂ Cl.

(4) non-semiconducting carrier material

Al ₂ O ₃ is preferred as the non-semiconducting carrier material.

(5) passivating substances

To prevent recombination of the electron and charge transport layer in the semiconducting metal oxide, a passivation layer may be provided on the semiconducting metal oxide. A passivation layer may be provided prior to adsorption of the amorphous material or composition comprising such material, or after the adsorption process. Suitable passivating materials are aluminum salts, Al ₂ O ₃ , silanes such as CH ₃ SiCl ₃ , metal organic complexes, in particular Al ³⁺ complexes, 4-tert-butyl pyridine, MgO, 4-guanidino butyric acid and hexadecyl horses. It is ronic acid. The passivation layer is preferably very thin.

(D) charge transport layer [step (iv)]

The charge transport layer may comprise an amorphous material according to the present invention or a composition comprising such material. The charge transport layer may include additional hole-transporting materials.

Suitable further hole-transporting materials are inorganic hole-transporting materials, organic hole-transporting materials or combinations thereof. Preferably, the additional hole-transporting material is in the solid state. Such compounds are known to those skilled in the art.

If the charge transport layer does not comprise an amorphous material according to the invention or a composition comprising such a material, the hole-transporting material of the photoelectric conversion element is preferably selected from the hole-transporting materials mentioned above as additional hole-transporting materials. do.

A method of forming the charge transport layer:

The charge transport layer may be provided, for example, by one of the following two methods. According to a first method, a counter electrode is first placed on the photosensitive layer, and then the material of the charge transport layer is applied in a liquid state to penetrate the gap between them. According to a second method, the charge transport layer is first disposed directly on the photosensitive layer, followed by the counter electrode.

When the wet charge transfer layer is provided by the second method, the wet charge transfer layer is applied to the photosensitive layer, and a counter electrode is disposed on the wet charge transfer layer without drying, the edges of which are, if necessary, liquid-leakage. treatment to prevent When the gel charge transfer layer is provided by the second method, the charge transfer material may be applied in a liquid state, and may be gelled by polymerization or the like. In this case, the counter electrode may be placed on the charge transfer layer before or after drying and fixing the charge transfer layer.

The charge transfer layer may be deposited by, for example, a roller method, an immersion method, an air-knife method, an extrusion method, a slide-hopper method, a wire-bar method, a spin method, a spray method, a cast method or a printing method. A suitable method is similar to the method of forming a semiconducting metal oxide layer or adsorbing an amorphous material to the semiconductor mentioned above.

When the charge transport layer is composed of one or more solid electrolytes, the solid hole transport material and the like can be formed by anhydrous film-forming methods such as physical vacuum deposition methods or CVD methods, followed by deposition of a counter electrode thereon. The hole-transporting material can be prepared to penetrate the photosensitive layer by a vacuum deposition method, a cast method, a coating method, a spin-coating method, a soaking method, an electrolytic polymerization method, a photo-polymerization method, a combination of these methods, and the like.

(E) counter electrode [step (v)]

As mentioned above, the counter electrode is a counter electrically conductive layer, which is optionally supported by a substrate as defined above. Examples of the electrically conductive material used for the counter electrically conductive layer include metals such as platinum, gold, silver, copper, aluminum, magnesium and indium; mixtures and alloys thereof, in particular mixtures and alloys of aluminum and silver; carbon; electrically conductive metal oxides such as indium-tin composite oxide and fluorine-doped tin oxide. Among these, platinum, gold, silver, copper, aluminum and magnesium are preferred, and silver or gold is particularly preferred. Specifically, silver is used. Also suitable electrodes are mixed inorganic/organic electrodes and polylayer electrodes, such as LiF/Al electrodes. Suitable electrodes are described, for example, in WO 02/101838 (particularly pages 18 to 20).

The substrate of the counter electrode is preferably made of glass or plastic which is coated or deposited by an electrically conductive material. The counter electrically conductive layer preferably has a thickness of 3 nm to 10 μm, although the thickness is not limited.

Light may be irradiated from either side or both sides of the electrically conductive layer provided in step (i) and the counter electrode provided in step (v), such that at least one of these substantially causes the light to reach the photosensitive layer. should be transparent with From the viewpoint of improving the electricity generation efficiency, it is preferable that the electrically conductive layer provided in step (i) is substantially transparent to incident light. In this case, the counter electrode preferably has light-reflecting properties. This counter electrode may consist of a deposited layer of metal or an electrically conductive oxide, or glass or plastic with a thin metal film. A device of this type, also referred to as a “concentrator”, is described, for example, in WO 02/101838 (in particular on pages 23 and 24).

The counter electrode may be disposed by directly applying an electrically conductive material to the charge transfer layer by metal-plating or vapor deposition (physical vapor deposition (PVD), CVD, etc.). Similar to the use of a conductive support, it is preferred that metallic lead be used to reduce the resistance of the counter electrode. Metallic lead is particularly preferably used for the transparent counter electrode. The preferred aspect of the metallic lead used in the counter electrode is the same as that of the metallic lead used in the above-mentioned conductive layer.

(F) other

One or more further functional layers, such as a protective layer and an anti-reflective layer, may be disposed on either or both of the conductive layer and/or the counter electrode. The functional layer may be disposed by a method selected according to the material used, such as a coating method, a vapor deposition method and an adhesion method.

(G) Internal structure of the photoelectric conversion element

The photoelectric conversion device may have various internal structures depending on the desired end use. Structures are classified into two main types: structures that enable light incidence from both sides, and structures that enable light incidence from only one side. In the first case, the photosensitive layer, the charge transport layer and optionally other layers are disposed between the transparent electrically conductive layer and the transparent counter electrically conductive layer. This structure enables light incident from both sides of the device. In the second case, one of the transparent electrically conductive layer and the transparent counter electrically conductive layer is transparent, while the other is not. Naturally, when the electrically conductive layer is transparent, light is absorbed from the side of the electrically conductive layer, whereas when the counter electrically conductive layer is transparent, light is absorbed from the side of the counter electrode.

Preferably, the photoelectric conversion element of the present invention is a component of a photovoltaic cell, more preferably a solar cell.

A photovoltaic cell is constructed by connecting a photoelectric conversion element to an external circuit to operate electrically or generate electricity in the external circuit. A photovoltaic cell having a charge transport layer composed of an ionically conductive material is referred to as a photo-electrochemical cell. Photovoltaic cells for power generation using sunlight are referred to as solar cells.

Accordingly, the photovoltaic cell is constructed by connecting to an external circuit of the photoelectric conversion element of the present invention to electrically operate or generate electricity in the external circuit. Preferably, the photovoltaic cell is a solar cell, ie a cell for power generation using sunlight.

The sides of the photovoltaic cell are preferably sealed with a polymer or adhesive or the like to prevent deterioration and volatilization of the contents of the cell. The external circuit is connected with the conductive support and the counter electrode through lead. A variety of known circuits can be used in the present invention.

When the photoelectric conversion element of the present invention is applied to a solar cell, the internal structure of the solar cell may be essentially the same as the internal structure of the above-mentioned photoelectric conversion element. The solar cell including the photoelectric conversion element of the present invention may have a known module structure. In a generally known module structure of a solar cell, the cell is placed on a substrate of metal, ceramic, or the like, and covered with a coating resin, protective glass, or the like, whereby light is introduced from the opposite side of the substrate. The solar cell module may have a structure in which the cell is positioned on a substrate of a transparent material such as tempered glass to introduce light from the side of the transparent substrate. Specifically, a super-straight type module structure, a substrate type module structure, a potting type module structure, and a substrate-integrated type module generally used in an amorphous silicon solar cell and the like The structure is known as a solar cell module structure. The solar cell comprising the photoelectric conversion element of the present invention may have, for example, a module structure appropriately selected from the above structures that can be adapted according to the individual requirements of a specific application.

The solar cell of the present invention may be used in a tandem cell. Accordingly, the present invention also relates to a stacked cell comprising the inventive solar cell and organic solar cell.

Stacked batteries are mainly known and are described, for example, in International Patent Publication No. 2009/013282. The stacked cell of the present invention can be prepared as described in WO 2009/013282, except that the solar cell of the present invention replaces the dye-sensitized solar cell described in the literature.

The amorphous materials of the present invention or compositions comprising such materials are advantageously suitable for field effect transistors (FETs). They can be used, for example, in the manufacture of integrated circuits (ICs), where conventional n-channel MOSFETs (metal oxide semiconductor field effect transistors) have been used heretofore. Here, these are, for example, CMOS-type semiconductor units for microprocessors, microcontrollers, static RAMs and other digital logic circuits. For the production of semiconductor materials, the amorphous material of the present invention may be further processed by one of the following processes: printing (offset, flexographic, gravure, screenprinting, ink-jet, electrophotography); Laser delivery, photolithography, drop-casting. They are particularly suitable for use in displays (specifically large-surface area and/or flexible displays), RFID tags, smart labels and sensors.

The amorphous materials of the present invention or compositions comprising such materials are also advantageously suitable as electronic conductors in field effect transistors (FETs), photoelectric conversion devices, in particular solar cells, and light emitting diodes (LEDs). They are also particularly advantageous as exciton transport materials in exciton solar cells.

The present invention also relates to a field effect transistor comprising a substrate having at least one gate structure, a source electrode and a drain electrode, and as semiconductor at least one amorphous material according to the invention or a composition comprising such material.

The present invention also relates to a substrate having a plurality of field effect transistors, wherein at least some of the field effect transistors comprise at least one amorphous material according to the present invention or a composition comprising such material.

The invention also provides an electroluminescent (EL) device comprising an upper electrode, a lower electrode, wherein at least one of said electrodes is transparent, an electroluminescent layer and optionally an auxiliary layer, wherein said electroluminescent device comprises at least one amorphous materials of the present invention or compositions comprising such materials. EL devices are characterized by the fact that they emit light when a voltage is applied by a flow of current. Such devices have long been known in industry and technology as light emitting diodes (LEDs). Light is emitted due to the fact that positive charges (holes) and negative charges (electrons) combine with the emission of light. In the sense of this application, the terms "electroluminescent device" and "light emitting diode (LED)" are used synonymously. In general, the EL device is composed of a plurality of layers. At least one layer contains at least one charge transport element. The layer structure is in principle as follows:

1. carrier, substrate;

2. base electrode (anode);

3. hole-injection layer;

4. hole-transport layer;

5. Emissive layer;

6. electron-transport layer;

7. electron-injection layer;

8. top electrode (cathode);

9. Contacts;

10. Covering, encapsulation.

This structure represents the most general case and can be simplified by omitting individual layers, as a result of which one layer performs several tasks. In the simplest case, the EL device consists of two electrodes in which an organic layer is arranged between the two electrodes, which satisfies all functions including emission of light. The structure and manufacturing method of the light emitting diode are similar to the structure and manufacturing method of an organic light emitting diode (OLED). Such structures and methods for their preparation are known to the person skilled in the art mainly from, for example, International Patent Publication No. 2005/019373. Suitable materials for the individual layers of the LED are disclosed, for example, in WO 00/70655. The disclosures of these documents are incorporated herein by reference. In principle, the LED according to the invention can be manufactured by methods known to the person skilled in the art. In a first aspect, an LED is fabricated by successive deposition of individual layers onto a suitable substrate. For the deposition, it is possible to use conventional techniques such as thermal evaporation, chemical vapor deposition and the like. In another embodiment, the layer, in particular the amorphous material of the present invention or a composition comprising such material, may be coated from a dispersion or solution in a suitable solvent, for which coating techniques known to those skilled in the art are used.

The amorphous materials of the present invention or compositions comprising such materials are advantageously suitable for thin film transistors (TFTs). To provide a thin film transistor, the amorphous material of the present invention or a composition comprising such material is preferably further processed by one of the following processes: printing (offset, flexographic, gravure, screen printing, ink-jet, electrophotography), laser transmission, photolithography, drop-casting.

The amorphous material of the invention is also advantageously suitable in light-emitting diodes (LEDs), in particular as semiconducting layers of light-emitting diodes or in semiconducting layers of light-emitting diodes. The amorphous materials of the present invention are also particularly suitable as phosphor materials of light-emitting diodes or in phosphor materials of light-emitting diodes.

The amorphous materials of the present invention are particularly suitable as charge transport materials. Specifically, the amorphous material of the present invention is suitable as a charge transport material in a battery. The amorphous materials of the present invention are particularly suitable as charge transport materials in rechargeable batteries (accumulators).

The invention is illustrated in detail with reference to the following non-limiting examples.

Example

Crystalline compounds in the extract and product mixtures were identified by X-ray powder diffraction, recorded at 25° C. using Cu-Ka radiation (1.54178 Å).

The melting behavior of the extract and product mixture was determined by differential scanning calorimetry (DSC) in an aluminum crucible under a nitrogen atmosphere at a heating rate of 20 K/min.

In a 100 mL reaction vessel, 3 g CH ₃ NH ₃ I, 0.546 g CH ₃ NH ₃ Cl and 1.499 g PbCl ₂ (molar ratio: 3.5 : 1.5 : 1) were heated to a temperature of 140° C. under a nitrogen atmosphere (heating rate). : 20 °C/min). The reaction mixture was then allowed to cool to room temperature (20° C.). Temperature dependent XRD measurements were performed. 1 shows the XRD of an extract mixture at room temperature (20° C.) before heating. At 140° C., a clear yellow melt with no solids content was obtained. 2 shows the XRD of the reaction mixture at 140° C. showing no reflection, indicative of the melt.

The obtained product was analyzed by DSC and XRD measurements. Surprisingly, the product had a low melting point of about 100° C. (melting point of the effluent: CH ₃ NH ₃ I = 240° C., CH ₃ NH ₃ Cl = 230° C., PbCl ₂ =500° C.). This low melting point is _{consistent with the observation that the main product is an amorphous material with composition 5 (CH 3} NH ₃ ): 1Pb: 3.5I: 3.5Cl according to elemental analysis. No mass loss was observed during the reaction. 3 shows the DSC measurements confirming the thermal behavior and also showing no mass loss. Amorphous materials are stable under an inert atmosphere.

In addition to solid state synthesis, it is also possible to prepare extracts or amorphous compounds in dimethylformamide (or other polar organic solvents), which is a suitable solvent for amorphous compounds. The reaction mixture was heated to 60° C. and kept at reflux for 1 hour. After evaporation of the solvent, the behavior was similar to the solid state synthesis, ie there was an amorphous phase with a low melting point of about 100 °C.

By substituting Sn for Pb, a similar behavior was observed. After heating to 120° C., an amorphous material having a low melting point was obtained using the same molar ratio (5: 1: 3.5: 3.5, CH ₃ NH _{3 : Sn: I: Cl).} The melting point of this mixture was detected by DSC measurement. The mixture started to melt above 70° C., and also no mass loss was observed.

Claims (25)

Amorphous material of the composition of formula (I):
Formula I
(R ¹ NR ² ₃ ) ₅ MeX ¹ _a X ² _b
In the above formula,
R ¹ is methyl or ethyl;
R ² are all hydrogen;
Me is Pb or Sn;
X ¹ and X ² have different meanings and are each independently selected from F, Cl, Br and I;
a and b are each independently 0 to 7, and the sum of a and b is 7. According to claim 1,
and R ¹ is methyl. According to claim 1,
X ¹ is I and X ² is Cl. According to claim 1,
wherein a and b are both 3.5. (CH ₃ NH ₃ ) ₅ PbI _3.5 Cl _3.5 or (CH ₃ NH ₃ ) ₅ SnI _3.5 Cl _3.5 Amorphous material. A composition comprising an amorphous material of the composition of formula (I) according to claim 1 :
Formula I
(R ¹ NR ² ₃ ) ₅ MeX ¹ _a X ² _b
In the above formula,
R ¹ , R ² , Me, X ¹ , X ² , a and b are as defined in claim 1 . A compound of formula I, which comprises reacting a compound of formula 1 A method for preparing an amorphous material of the composition:
Formula 1
(R ¹ NR ² ₃ )X ¹
Formula 2
(R ¹ NR ² ₃ )X ²
Formula 3
MeX ² ₂
Formula I
(R ¹ NR ² ₃ ) ₅ MeX ¹ _a X ² _b
In the above formula,
R ¹ is methyl or ethyl;
R ² are all hydrogen;
Me is Pb or Sn;
X ¹ and X ² have different meanings and are each independently selected from F, Cl, Br and I;
a and b are each independently 0 to 7, and the sum of a and b is 7. 8. The method of claim 7,
A process for preparing a method in which the components are mixed in a ratio corresponding to the stoichiometric amounts of the elements of the composition 5(R ¹ NR ² ₃ ) : 1Me : aX ¹ : bX ^{2 .} 8. The method of claim 7,
(R ¹ NR ² ₃ )X ¹ : (R ¹ NR ² ₃ )X ² : MeX ² ₂ molar ratio of 3.5 : 1.5 : 1. 10. The method according to any one of claims 7 to 9,
A method for preparing an amorphous material having the composition of _{(CH 3} NH ₃ ) ₅ PbI _3.5 Cl _3.5 , comprising reacting (CH ₃ NH ₃ )I, (CH ₃ NH ₃ )Cl and PbCl _{2 .} 10. The method according to any one of claims 7 to 9,
A method for preparing an amorphous material having a composition of _{(CH 3} NH ₃ ) ₅ SnI _3.5 Cl _3.5 , comprising reacting (CH ₃ NH ₃ )I, (CH ₃ NH ₃ )Cl and SnCl _{2 .} A photoelectric conversion device comprising at least one amorphous material according to any one of claims 1 to 5 or a composition according to claim 6 . 13. The method of claim 12,
an electrically conductive layer that is part of or forms the working electrode (anode);
a photosensitive layer comprising an absorber material and optionally comprising a semiconducting metal oxide or insulating material;
charge transfer layer; and
An electrically conductive layer that is part of the counter electrode (cathode) or forms the counter electrode (cathode)
A photoelectric conversion device comprising: said photosensitive layer and/or said charge transport layer comprising said at least one amorphous material or said composition. 14. The method of claim 13,
A photoelectric conversion device, wherein the photosensitive layer comprises the at least one amorphous material or the composition as an absorber material. 14. The method of claim 13,
A photoelectric conversion device, wherein the photosensitive layer comprises at least one perovskite material as an absorber material. 14. The method of claim 13,
A photoelectric conversion device further comprising a hole-conducting layer between the charge transport layer and the cathode. A solar cell comprising the photoelectric conversion element according to claim 12 . A field effect transistor (FET) comprising a substrate having at least one gate structure, a source electrode and a drain electrode, and at least one amorphous material according to any one of claims 1 to 5 or a composition according to claim 6 . A substrate comprising a plurality of field effect transistors, wherein at least a portion of the field effect transistors comprise at least one amorphous material according to claim 1 or a composition according to claim 6 . A top electrode, a bottom electrode, an electroluminescent layer and optionally an auxiliary layer, comprising at least one amorphous material according to any one of claims 1 to 5 or a composition according to claim 6, wherein the top electrode and at least one of the lower electrodes is transparent. 21. The method of claim 20,
An electroluminescent device in the form of a light emitting diode (LED). 6. The method according to any one of claims 1 to 5,
Amorphous materials for use in semiconducting layers in thin film transistors (TFTs), semiconducting layers in light emitting diodes (LEDs), phosphor materials in LEDs, or charge transport materials in batteries or rechargeable batteries. 7. The method of claim 6,
A composition for use in a semiconducting layer of a thin film transistor (TFT), a semiconducting layer of a light emitting diode (LED), a phosphor material of an LED, or a charge transport material of a battery or rechargeable battery. delete delete

Images